Dioxocyclohexanecarboxanilide insecticides and acaricides

ABSTRACT

The present invention relates to certain carboxanilide insecticidal and acaricidal methods and compositions. It further relates to certain carboxanilides employed as active ingredients therein.

This application is a continuation-in-part of our copending divisional application, Ser. No. 412,088 filed on Nov. 2, 1973, now abandoned, which in turn is a divisional of Ser. No. 197,967, filed on Nov. 11, 1971, now U.S. Pat. No. 3,801,630, issued on Apr. 2, 1974, which patent is a continuation-in-part of Ser. No. 106,933, filed on Jan. 15, 1971, now abandoned.

The present invention relates to certain novel carboxanilides. It further relates to the use of certain known carboxanilides and the novel carboxanilides as insecticides and acaracides. It further relates to the synthesis of the carboxanilides through the reaction of a 1,3-cyclohexanedione with a phenylisocyanate or phenylisothiocyanate.

The carboxanilides useful as insecticides and acaracides in the present invention may be represented by the following structure: ##SPC1##

Wherein R and R₁ are each selected from the group consisting of hydrogen, lower alkyl (C₁ -C₄), phenyl, halophenyl, and benzyl; R₂ is sulfur or oxygen; R₃ and R₄ are each selected from the group consisting of hydrogen, lower alkyl (C₁ -C₄) and phenyl; W is hydrogen or halogen; X is hydrogen, halogen, lower alkyl (C₁ -C₄), halo-substituted lower alkyl (C₁ -C₄), lower alkoxy (C₁ -C₄), lower alkylthio (C₁ -C₄), or nitro; Y is hydrogen, halogen, lower alkyl (C₁ -C₄) or halo-lower alkyl (C₁ -C₄); and Z is hydrogen or halogen.

Suitable lower alkyl substituents include, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl groups. The corresponding alkoxy and alkylthio groups are also suitable for use in the present invention. Suitable halogen substituents include, for example, fluoro, chloro, bromo and iodo groups. Suitable lower carbalkoxy groups include, for example, carbomethoxy, carbethoxy, carbopropoxy and carbobutoxy groups.

Suitable halo substituted lower alkyl groups include, for example, ennechlorobutyl, heptachloropropyl, 2,2,2-trichloroethyl, 2,2,2-tribromoethyl, 2,2-dichloroethyl, 2-fluoroethyl, 2-bromoethyl, 2-chloroethyl, chlorodifluoromethyl, chloromethyl, bromomethyl, fluoromethyl, and the like. Of the numerous suitable halo substituted lower alkyl substituents, a few of which are mentioned above, the trihalomethyl substituents are especially preferred. Within this preferred group one may mention trichloromethyl and trifluoromethyl as being especially preferred.

Suitable halophenyl groups include, for example, the ortho and para, mono and disubstituted bromo and chlorophenyl groups. Parachlorophenyl substituents are among the preferred.

The carboxanilides which are employed in the pesticidal methods of the present invention have the formula: ##SPC2##

Wherein R and R₁ are each selected from the group consisting of hydrogen, phenyl, halophenyl, benzyl and lower alkyl (C₁ -C₄); R₂ is sulfur or oxygen; R₃ and R₄ are each selected from the group consisting of hydrogen, lower alkyl (C₁ -C₄) and phenyl; W is hydrogen or halogen; X is hydrogen, halogen, lower alkyl (C₁ -C₄), halo-substituted lower alkyl (C₁ -C₄), lower alkoxy (C₁ -C₄), lower alkylthio (C₁ -C₄), cyano, carb-lower alkoxy (C₁ -C₄) or nitro; Y is hydrogen, halogen, lower alkyl (C₁ -C₄) or halo-lower alkyl (C₁ -C₄) and when X and Y are taken together they can form a benzo group; and Z is hydrogen or halogen. Known carboxanilides within this class are discussed, for example, by N. Rogers et al., J. Chem. Soc., page 341(1955) and by T. Ukita et al., Chem. Pharm. Bull. (JAP), 8, 1016-20(1960).

The synthetic process for the preparation of the curboxanilides employed in the pesticidal process involves the reaction of a 1,3-cyclohexanedione with a phenylisocyanate or a phenylisothiocyanate. The reaction is generally carried out in the presence of a tertiary organic amine, with or without an organic solvent. Elevated temperatures are generally employed to facilitate the reaction. Temperatures in the range of from about 30°C. to about 150°C. are generally suitable, with temperatures in the range of from about 50°C. to about 100°C. being preferred. Following the period of heating, which will usually be under reflux, the carboxanilide may be precipitated by the addition of an aqueous solution of mineral acid. The product may then be recovered from the mixture by any convenient means, as, for example, by filtration, centrifugation or the like. If desired, purification can be effected by redissolving the product in a solvent of moderate polarity, such as ethyl ether, a C₁ -C₄ alcohol, cyclohexane, methylene chloride, or the like and filtering off the insoluble material. The desired carboxanilide can be recovered from the filtrate by evaporation. This synthetic reaction scheme may be graphically illustrated as follows: ##SPC3##

The isocyanates and isothiocyanates employed in the preparation of the carboxanilides may be conveniently prepared from the appropriate anilides by reaction with phosgene or thiophosgene. Typical procedures for these general reactions are set forth by S. Petersen et al., Chemische Berichte, 81, page 31-8(1948), C.A., 43, page 169a; E. Dyer et al., JACS, 54, 777/87(1932); Wagner and Zook, Synthetic Organic Chemistry, pages 640 and 827-30, John Wiley & Sons, Inc. (1953).

For use as insecticides or acaricides, the carboxanilides are formulated and applied by conventional methods to the foliage of plants to protect them from pests which feed thereon, or to the soil to protect plants from soil-borne pests as well as warm-blooded animals, such as farm, domestic, zoo and laboratory animals, to protect them against and/or rid them of insect and acarid infection. They may also be applied to breeding sites of the insects and acaricides to control the egg, larvae and adult stages of breeding pest populations. In this regard, 4'-chloro-2-hydroxy-6-oxo-1-cyclohexene-1-carboxanilide is preferred as a larvicidal and ovicidal agent for the control of insects and acarids. These compounds are advantageously formulated as dusts, dust concentrates, emulsifiable liquids, wettable powders and the like.

The dusts are usually prepared by simply grinding together from about 1% to 15% by weight of the active carboxanilide with a finely divided inert diluent such as walnut flour, diatomaceous earth, fullers earth, attaclay, talc, or kaolin. Dust concentrates are made in similar fashion, excepting that about 16% to 75% by weight of active ingredient is ground together with the diluent. In practice, this concentrate is then generally admixed at the site of use with more inert diluent before it is applied to the plant foliage or animals which are to be protected from insect and acarid attack.

Wettable powders are generally prepared in the same manner as dust concentrates, but usually about 1% to 5% by weight of a dispersing agent, for example an alkali metal lignosulfonate and about 1% to 5% of a surfactant, such as alkyl phenoxy polyethylene ethanol, naphthalene sulfonic acid condensate, or an ester of sodium isothionate, is incorporated in the formulation. For application to agronomic crops, shrubs, ornamentals, and the like, the wettable powder is usually dispersed in water and applied as a spray. For treatment of warm-blooded animals, the same spray type application may be used or the wettable powder may be dispersed in the water of a dipping trough through which the animals are driven.

The emulsifiable liquids may be prepared by dissolving the active compound in an organic solvent, such as acetone, and admixing the thus formed solution with other organic solvents, such as cyclohexanone and toluene containing an emulsifier such as calcium dodecylbenzene sulfonate or an alkylaryl polyether alcohol. The emulsifiable liquid is then generally dispersed in water for spray or dip application.

In practice, we have found that the compounds of the present invention in which at least one of X, Y or Z represents a substituent other than hydrogen, are preferred for use in controlling acarids. Moreover, we have found the mono-, di-, and trihalosubstituted carboxanilides, particularly the mono-, di- and tri-chloro carboxanilides, are most effective for inhibiting or reducing tick infestations on warm-blooded animals.

The present invention is further illustrated by the examples set forth below which are not to be taken as limitative thereof. In each case, parts are by weight unless otherwise indicated.

EXAMPLES 1-19 Preparation of 3',4'-Dichloro-2-Hydroxy-6-Oxo-1-Cyclohexene-1-Carboxanilide and Related Compounds

A solution containing 1,3-cyclohexanedione, 144 parts, 3,4-dichlorophenylisocyanate, 240 parts, in pyridine, 800 parts, is heated at 110°-115°C. for 2 hours. After cooling, the mixture is poured with stirring into a solution containing 2000 parts of concentrated hydrochloric acid in 7500 parts of cold water. A solid formed which is collected and washed on the filter with cold water and dried in a vacuum oven at 50°C. The pure carboxanilide is obtained by crystallization from 7000 parts of ethyl alcohol to give 242 parts of light tan colored crystals, melting point 131°-132°C.

The compounds of Table I having the structure set forth below are prepared by essentially the same procedure as above using the appropriately substituted isocyanate in place of the 3,4-dichlorophenylisocyanate. Reaction periods vary from 2 to 4 hours at temperatures usually of 95°-100°C. In cases where appreciable amounts of substituted carbanilides corresponding to the isocyanates are formed, purification is further effected by dissolving the carboxanilide in a solvent of moderate polarity, such as ethyl ether or methylene chloride, filtering off the insoluble carbanilide, and recovering the product from the filtrate by evaporation of the solvent.

                                      Table I                                      __________________________________________________________________________                             Analysis                                               Substituents   Melting  Calculated   Found                                     Example                                                                              X     Y  Point    C    H   N   C    H   N                                __________________________________________________________________________     2    3-Cl 4-Cl                                                                               131°C.-132°C.                                                              52.02                                                                               3.69                                                                               4.66                                                                               51.78  3.37                                                                             4.83                             3    2-Cl 5-Cl                                                                               123°C.-125°C.                                                              52.02                                                                               3.69                                                                               4.66                                                                               52.09  3.66                                                                             4.78                             4    2-Cl 4-Cl                                                                               174°C.-175°C.                                                              52.02                                                                               3.69                                                                               4.66                                                                               52.26  3.60                                                                             4.95                             5    2-F  H   124°C.-125°C.                                                              62.67                                                                               4.82                                                                               5.62                                                                               63.17  4.83                                                                             5.70                             6    3-F  H   84°C.-85°C.                                                                62.67                                                                               4.82                                                                               5.62                                                                               63.34  4.86                                                                             5.28                             7    4-F  H   110°C.-111°C.                                                              62.67                                                                               4.82                                                                               5.62                                                                               62.39  4.83                                                                             5.62                             8    4-Br H   104°C.-105°C.                                                              50.34                                                                               3.90                                                                               4.52                                                                               50.38  3.93                                                                             4.70                             9    4-CH.sub.3                                                                          H   113°C.-114°C.                                                              68.55                                                                               6.17                                                                               5.71                                                                               68.28  6.33                                                                             5.44                             10   2-C.sub.2 H.sub.5                                                                   H   78°C.-80°C.                                                                69.48                                                                               6.61                                                                               5.40                                                                               69.62  6.76                                                                             5.23                             11   2-CH.sub.3                                                                          3-Cl                                                                               121°C.-122°C.                                                              60.11                                                                               5.04                                                                               5.01                                                                               60.11  5.02                                                                             5.01                             12   2-CH.sub.3                                                                          4-Cl                                                                               155°C.-156°C.                                                              60.11                                                                               5.04                                                                               5.01                                                                               60.19  5.04                                                                             4.79                             13   3-Cl 4-CH.sub.3                                                                         108°C.-109°C.                                                              60.11                                                                               5.04                                                                               5.01                                                                               59.99  5.18                                                                             4.95                             14   2-CH.sub.3                                                                          4-Br                                                                               158°C.-159°C.                                                              51.87                                                                               4.35                                                                               4.32                                                                               52.08  4.38                                                                             4.27                             15   4-I  H   122°C.-123°C.                                                              43.72                                                                               3.39                                                                               3.92                                                                               43.82  3.40                                                                             3.83                             16   4-CH.sub.3 S                                                                        H    99°C.-100°C.                                                              60.62                                                                               5.45                                                                               5.05                                                                               60.45  5.40                                                                             5.21                             17   2-CF.sub.3                                                                          H   85°C.-86°C.                                                                56.19                                                                               4.04                                                                               4.68                                                                               56.17  3.99                                                                             4.55                             18   3-CF.sub.3                                                                          H   102°C.-103°C.                                                              56.19                                                                               4.04                                                                               4.68                                                                               56.32  4.18                                                                             4.67                             19   3-CF.sub.3                                                                          5-CF.sub.3                                                                         119°C.-121°C.                                                              49.06                                                                               3.02                                                                               3.81                                                                               49.52  3.05                                                                             3.25                             __________________________________________________________________________

EXAMPLE 20 Preparation of 2'-Fluoro-2-Hydroxy-6-Oxo-1-Cyclohexene-1-Carboxanilide ##SPC4##

To 6.0 grams of 1,3-cyclohexanedione (0.054 mole) and 5.9 grams of triethylamine (0.059 mole) dissolved in 150 ml. of dry acetone, is added 7.4 grams of o-fluorophenylisocyanate (0.054 mole). The mixture is heated to reflux until none of the isocyanate is visible by infrared spectrophotometry (requires 1 to 3 hour). The orange solution is concentrated, and taken up in chloroform. The chloroform is washed with a dilute aqueous solution of hydrochloric acid, and is dried with magnesium sulfate. Concentration by evaporation yielded 5.0 grams of gummy orange solids. Recrystallization from cyclohexane yields 4.0 grams of the desire product in the form of white crystals; melting point 124°C.- 125.5°C. Infrared spectrophotometry and nuclear magnetic resonance spectrometry confirm the structural assignment of the product as 2'-fluoro-2-hydroxy-6-oxo-cyclohexene-1-carboxanilide.

EXAMPLE 21 Preparation of 3'-Chloro-2-Hydroxy-6-Oxo-1-Cyclohexene-1-Carboxy-o-Toluidide ##SPC5##

A solution containing 11.2 parts of cyclohexane-1,3-dione and 16.8 parts of 3-chloro-o-tolylisocyanate in pyridine, 100 parts, is heated at 90°C.-100°C. for two hours and then allowed to cool to room temperature. The resulting light slurry is poured into 350 parts of cold 2-normal hydrochloric acid and the crude product is recovered by filtration. The damp solid is dissolved in 600 parts of ethyl alcohol and filtered from 2.9 parts of insoluble solid. The filtrate is chilled on an ice-water bath to precipitate the desired product, which is then filtered to give 17.1 parts of pale buff platelets, melting point 120.5°C.-121.5°C.

Analysis Calculated for C₁₄ H₁₄ ClNO₃ : C, 60.11 H, 5.04; Cl, 12.68; N, 5.01. Found: C, 60.11; H, 5.02; Cl, 12.75; N, 5.01.

EXAMPLES 22-43 Preparation of 4'-Chloro-2-Hydroxy-6-Oxo-1-Cyclohexene-1-Carboxanilide and Related Compounds ##SPC6##

A solution containing 8.5 parts of cyclohexane-1,3-dione, 11.5 parts of p-chlorophenylisocyanate and 7.6 parts of triethylamine in 200 parts of acetone is stirred and refluxed for two hours. The infrared spectrum then shows no isocyanate (band at 2270 cm.sup.⁻¹). The solution is concentrated under reduced pressure to about 50 parts, with separation of a few crystals, and poured with stirring into 500 parts of 2-normal hydrochloric acid. The precipitated solid is collected by filtration and dried. The resulting solid is mixed with chloroform, 250 parts by volume, and filtered from 6.5 parts of insoluble by-product. Removal of chloroform from the filtrate leaves a light pink solid which is crystallized from alcohol to give 6.7 parts of nearly white solid, melting point 113°C.-114°C.

Analysis Calculated for C₁₃ H₁₂ ClNO₃ : C, 58.76; H, 4.56; Cl, 13.34; N, 5.27. Found: C, 58.74; H, 4.55; Cl, 13.16; N, 4.97.

The same product is obtained as a light red powder when the reaction is run in pyridine. Yield, 11.6 parts of recrystallized product.

The compounds of Table II, having the structure set forth below, are prepared by essentially the same procedure, using the appropriately substituted phenylisocyanates for the p-chlorophenylisocyanate used therein.

                  TABLE II                                                         ______________________________________                                         Substituents       Melting        %                                            Example                                                                                X            Y     Point        Yield                                  ______________________________________                                         23     3-Cl        4-Cl    131°C.-132°C.                                                                 62                                     24     3-Cl        H       92.5°C.-94°C.                                                                 56                                     25     4-Cl        H       113°C.-114°C.                                                                 58                                     26     4-Cl        2-CH.sub.3                                                                             155°C.-156°C.                                                                 49                                     27     2-Cl        4-NO.sub.2                                                                             267°C.-267.5°C.                                                               43                                     28     3-Cl        4-CH.sub.3                                                                             108°C.-109°C.                                                                 20                                     29     4-I         H       122°C.-123°C.                                                                 54                                     30     4-Br        2-CH.sub.3                                                                             158°C.-159°C.                                                                 42                                     31     2-Cl        4-Cl     174°C.-175.5°C.                                                              38                                     32     4-CH.sub.3  H       112.5°C.-114°C.                                                               44                                     33     2-C.sub.2 H.sub.5                                                                          H       78°C.-80°C.                                                                   34                                     34     4-Br        H       104°C.-105°C.                                                                 44                                     35     4-F         H       110°C.-111°C.                                                                 47                                     36     4-SCH.sub.3 H       99°C.-100°C.                                                                  43                                     37     2-CF.sub.3  H       84.5°C.-85.5°C.                                                               60                                     38     3-CF.sub.3  H       102°C.-103°C.                                                                 75                                     39     3-F         H        84°C.-84.5°C.                                                                62                                     40     3-CF.sub.3  5-CF.sub.3                                                                             119°C.-121°C.                                                                 36                                     41     4-Cl        3-NO.sub. 2                                                                            149.5°C.-150.5°C.                                                             66                                     42     3-Cl        2-CH.sub.3                                                                             120.5°C.-121.5°C.                                                             61                                     43     4-O--CO--CH.sub.3                                                                          H       160.5°C.-161.5°C.                                                             40                                     ______________________________________                                    

EXAMPLES 44-53 Insecticidal Activity

The efficacy of the compounds of the present invention for controlling insects is demonstrated by the following tests, wherein aphids and armyworms are used as test species. The procedures employed are as follows. Results obtained are reported in Table III.

Southern Armyworm (Prodenia eridania Cram.)

Compounds to be tested are made up as 0.1% solutions in a 65% acetone -- 35% water mixture. Sieva lima bean leaves are dipped in the test solution and set in the hood to dry. When dry, they are placed in four-inch petri dishes which have a moist filter paper in the bottom, and then third-instar armyworm larvae about 3/8 inch long are added to each dish. The dishes are covered and held at 80°F., 60% R.H. After 2 days, mortality counts and estimates of the amount of feeding are made.

Nasturtium Aphids (Aphis rumicis L.)

The compounds to be tested are made up as 0.1% solutions in a 65% acetone -- 35% water mixture. Three-inch pots containing a nasturtium plant two inches tall and infested two days before are selected for testing. The pots are placed on a turntable (4 RPM) and sprayed for two revolutions with an atomizer at 20 psi. air pressure. The spray tip is held about six inches from the plants and the spray is directed so as to give complete coverage of the aphids and the plants. The sprayed plants are laid on their side on white enamel trays which have had the edges coated with oil as a barrier. Mortality estimates are made after holding for two days at 70°F.

                                      TABLE III                                    __________________________________________________________________________                                     % Mortality                                                                    Southern                                                                            Nasturtium                                Example                                                                             Compound                   Armyworm                                                                            Aphids                                    __________________________________________________________________________     44                              100   90                                       45                               40   95                                       46                              100  100                                       47                               70  100                                       48                              100  100                                       49                               90   98                                       50                               90   98                                       51                               60  100                                       52                              100  100                                       53                              0    100                                       __________________________________________________________________________

EXAMPLES 54-59

The efficacy of the compounds of the present invention against spider mites is demonstrated in the following tests using the procedure set forth below. The results achieved are shown in Table IV below.

Two-Spotted Spider Mite (Tetranychus telarius L.)

Compounds to be tested are made up as 0.1% solutions in a 65% acetone -- 35% water mixture. Sieva lima bean plants with the first pair of leaves 3 to 4 inches in size are infested about 5 hours before testing, using about 100 to 200 adult mites per leaf. The infested leaves are dipped in the test solutions (in four-inch crystallizing dishes) for 3 seconds, and the plants set in the hood to dry. The treated plants are held for two days at 80°F., 60% R.H., and the adult mite mortality calculated by counting dead and alive adults on one leaf under the 10X binocularscope. The other leaf is held an additional 5 days and then is examined at 10X power to estimate the kill of eggs and newly-hatched nymphs, giving a measure of ovocidal and residual action, respectively.

                  TABLE IV                                                         ______________________________________                                                                  % Mortality                                           Example    Substituents  Spider Mites                                          ______________________________________                                         54         3,4-di-Cl     100                                                   55         3,6-di-Cl     100                                                   56         3-Cl          100                                                   57         4-Cl          100                                                   58         4-I           100                                                   59         2,4-di-Cl      50                                                   ______________________________________                                    

EXAMPLES 60-78

Effective control of acarina larvae is demonstrated in the following tests with larvae of Boophilus microplus, a one-host tick which can remain on a single host through its three life stages, i.e., larvae, nymph and adult. In these tests, a 10% acetone -- 90% water mixture contains from 1.0 to 100 ppm. of test compound. Twenty larvae are enclosed in a pipet sealed at one end with a gauze material and solution containing the test compound is then drawn through the pipet with a vacuum hose simulating a spray system. The ticks are then held for 48 hours at room temperature and mortality is determined. The results achieved are set forth in Table V below.

                  TABLE V                                                          ______________________________________                                         Substituents                ppm of Active                                      Example                                                                                X         Y      % Mortality                                                                             Ingredient                                   ______________________________________                                         60     2-Cl     4-Cl      80      1.0                                          61     3-Cl     4-Cl     100      10.0                                                                  100      3.3                                          62     2-Cl     5-Cl     100      10.0                                         63     4-Cl     2-CH.sub.3                                                                              100      10.0                                         64     3-Cl     4-CH.sub.3                                                                              100      10.0                                         65     4-Cl     3-NO.sub.2                                                                               80      33.0                                         66     5-Cl     6-CH.sub.3                                                                              100      3.3                                          67     4-Br     H         80      33.0                                         68     4-Br     2-CH.sub.3                                                                              100      3.3                                          69     4-I      H        100      10.0                                         70     3-F      H         80      3.3                                          71     4-F      H        100      33.0                                         72     2-CF.sub.3                                                                              H        100      33.0                                         73     3-CF.sub.3                                                                              H        100      33.0                                                                  100      33.0                                         74     3-CF.sub.3                                                                              5-CF.sub.3                                                                              100      10.0                                         75     4-CH.sub.3                                                                              H         80      33.0                                         76     2-C.sub.2 H.sub.5                                                                       H        100      100.0                                                                 100      50.0                                         77     4-SCH.sub.3                                                                             H        100      33.0                                         78     H        H        100      100.0                                                                 100      50.0                                         ______________________________________                                    

EXAMPLES 79-82

The efficacy of the compounds of the invention for controlling acarine nymphs is demonstrated following the same procedure used in Example 60, but substituting 10 nymphs of the three-host tick, Amblyomma americanum, for the 20 Boophilus larvae. Compounds are tested at from 10 ppm to 100 ppm of active ingredient in 10% acetone aqueous solution. The results achieved are reported in Table VI below.

                  TABLE VI                                                         ______________________________________                                         Substituents                ppm of Active                                      Example                                                                               X        Y        % Mortality                                                                             Ingredient                                   ______________________________________                                         79     3-Cl     4-Cl     100      10                                           80     3-Cl     H        100      33                                           81     4-Cl     H        100      10                                           82     2-F      H         70      100                                          ______________________________________                                    

EXAMPLES 83-96

Efficacy of the compounds of the present invention for the control of adult ticks is demonstrated in the following tests wherein adult Boophilus microplus ticks which have dropped from cattle are collected and used for testing.

Compound to be tested is dissolved in a 35% acetone -- 65% water mixture in sufficient amount to provide from about 40 to 2000 ppm of compound in the test solution. Ten ticks per treatment are used and they are immersed in test solution for 3 to 5 minutes, then removed and placed in cages and held at room temperature for three days. Mortality counts are then made and recorded. For these tests, non-resistant ticks as well as ethion-resistant and dioxathion-resistant ticks are used since the latter two are among the most difficult of their kind to control. Results of these tests are given in Table VII below.

                                      TABLE VII                                    __________________________________________________________________________                                  % Mortality                                       Substituents         ppm of Active                                                                          Ethion                                                                               Dioxathion                                                                           Non-                                  Ex.                                                                               R   R.sub.1                                                                            X    Y    Ingredient                                                                             Resistant                                                                            Resistant                                                                            Resistant                             __________________________________________________________________________     83 H   H   3-Cl H    2000     80    50   --                                    84 H   H   4-Cl H    1000    100   100   --                                                         500      20    50   --                                    85 H   H   3-Cl 4-CH.sub.3                                                                          2000     50    10   --                                    86 H   H   3-Cl 4-Cl 1900    100   100   --                                                         800      50   100   --                                                         40       10    40   --                                    87 CH.sub.3                                                                           CH.sub.3                                                                           H    H    2000     90    80   --                                    88 H   H   3-Cl H    1000    --    --    100                                   89 H   H   4-Cl H    1000    --    --    100                                   90 H   H   3-Cl 4-Cl 330     --    --    100                                                        100     --    --     10                                   91 H   H   4-Cl 2-CH.sub.3                                                                          1000    --    --    100                                   92 H   H   3-Cl 4-CH.sub.3                                                                          1000    --    --    100                                   93 H   H   2-Cl 3-Cl                     No test                               94 CH.sub.3                                                                           CH.sub.3                                                                           2-Cl 3-Cl                     No test                               95 H   H   p-oMe                                                                               H                        No test                               96 CH.sub.3                                                                           CH.sub.3                                                                           p-oMe                                                                               H                        No test                               __________________________________________________________________________

EXAMPLES 97-101

Following the procedures set forth in Examples 60 through 78 and 79 through 82 above, the following data were obtained.

                                      TABLE VIII                                   __________________________________________________________________________                           ppm. of                                                                              Boophilus                                                                            Amblyomma                                    Substituents          Active                                                                               microplus                                                                            americanum                                   Example                                                                             R   R.sub.1                                                                            X    Y   Ingredient                                                                           (larvae)                                                                             Nymphs                                       __________________________________________________________________________     97   CH.sub.3                                                                           CH.sub.3                                                                           H    H   20    --    100                                          98   H   H   2-Cl 3-Cl                                                                               10    100   --                                           99   CH.sub.3                                                                           CH.sub.3                                                                           2-Cl 3-Cl                                                                               80    100   --                                           100  H   H   p-OCH.sub.3                                                                         H   100   100   --                                           101  CH.sub.3                                                                           CH.sub.3                                                                           p-OCH.sub.3                                                                         H   100   100   --                                           __________________________________________________________________________

EXAMPLES 102-139 Preparation of Dioxocyclohexanecarboxanilides ##SPC7##

wherein R₂ is O or S

Following the procedure of Example 20, equimolar quantities (0.064 moles) of the appropriate dione, isocyanate or isothiocyanate and triethylamine in 160 ml. of dry acetone are heated at reflux for about 9 hours. The mixture is filtered and the filtrate is poured on ice and stirred to afford a first crop of the carboxanilide. This is then collected and the filtrate is acidified to pH 4 with concentrated hydrochloric acid to afford a second crop, which is collected. The combined crops are then recrystallized from appropriate solvents such as alcohols, alcohol-water, or acetone. Compounds prepared by this procedure are listed in Table IX below by structure with their melting points and recrystallization solvents.

                                      TABLE IX                                     __________________________________________________________________________                                        Melting                                                                              Recrystal-                            Example                            Point lization                              Number                                                                              Structure                     °C.                                                                           Solvent                               __________________________________________________________________________     102                                142.5-                                                                               Acetone                                                                  143.5                                       103                                227-228                                                                              Acetone                               104                                --                                          105                                78-80 Hexane                                106                                94.5-97                                                                              95% EtOH                              107                                101-104                                                                              95% EtOH                              108                                120-124                                                                              95% EtOH                              109                                157-  Me.sub.2 CO/-                                                            159.5 95% EtOH                              110                                116.5-                                                                               95% EtOH                                                                 119                                         111                                114-  95% EtOH                                                                 116.5 ether                                 112                                95-97 95% EtOH                              113                                109-111                                                                              MeOH ether                            114                                122-125                                                                              MeOH                                  115                                148-  MeOH                                                                     150.5                                       116                                86.5- 95% EtOH                                                                 88.5                                        117                                155-  95% EtOH                                                                 157.5                                       118                                143-146                                                                              95% EtOH                              119                                93.5-96                                                                              95% EtOH                              120                                154-156                                                                              95% EtOH                              121                                140-143                                                                              95% EtOH                              122                                212-215                                                                              Me.sub.2 CO/-                                                                  95% EtOH                              123                                203-  Me.sub.2 CO                                                              205.5                                       124                                129.5-                                                                               MeOH                                                                     132                                         125                                117-120                                                                              MeOH                                  126                                157-159                                                                              95% EtOH                              127                                183-  Me.sub.2 CO                                                              186.5                                       128                                147-  95% EtOH                                                                 149.5                                       129                                118.5-                                                                               95% EtOH                                                                 120.5                                       130                                148.5-                                                                               95% EtOH                                                                 150.5                                       131                                153-156                                                                              95% EtOH                              132                                114-  95% EtOH                                                                 115.5                                       133                                167-170                                                                              95% EtOH                              134                                174-177                                                                              95% EtOH                              135                                144-147                                                                              MeOH                                  136                                151-153                                                                              95% EtOH                              137                                184-187                                                                              Me.sub.2 CO                           138                                157.5-                                                                               2B EtOH                                                                  159                                         139                                138-141                                                                              MeOH                                  __________________________________________________________________________

EXAPLES 140-171 Preparation of Dioxocyclohexanecarboxanilides ##SPC8##

wherein R₂ is O or S

The dione (0.03 mole) is dissolved or suspended in 25 ml. of dry methyl ethyl ketone and stirred. The isocyanate or isothiocyanate (0.033 mole or 10% excess) is dissolved in 4 ml. of methyl ethyl ketone and added to the mixture. To this is added a catalytic amount (about two drops) of triethylamine. The mixture is then refluxed for about 2 hours and cooled to afford the carboxanilide, which is collected and washed with ethyl ether. Occasionally, the product will not crystallize from the reaction mixture, and hence, the mixture is evaporated to dryness to afford the crude carboxanilide. The product is then recrystallized from appropriate solvents such as alcohols, alcohol-water mixtures, or acetone. Compounds prepared by this procedure are listed in Table X below by structure with their melting points and recrystallization solvents.

                                      TABLE X                                      __________________________________________________________________________                                           Melting                                                                              Recrystal-                         Example                               Point lization                           Number                                                                              Structure                        °C.                                                                           Solvent                            __________________________________________________________________________     140                                   233-236                                                                              DMF                                                                      dec.                                     141                                   175.5-                                                                               95% EtOH                                                                 179                                      142                                   137.5-                                                                               95% EtOH                                                                 139                                      143                                   126-131                                                                              95% EtOH                           144                                   183-184                                                                              2B EtOH                            145                                   98.5- 95% EtOH                                                                 101                                      146                                   127.5-                                                                               95% EtOH                                                                 130                                      147                                   155-160                                                                              Me.sub.2 CO                        148                                   129-134                                                                              2B EtOH                            149                                   198-200                                                                              EtOAc                              150                                   105.5-                                                                               MeOH                                                                     111.5                                    .sup.≧                         76-78 95% EtOH                           152                                   86-93 MeOH                               153                                   147-150                                                                              Me.sub.2 CO                        154                                   191-  EtOAC                                                                    194.5                                    155                                   131-  2B EtOH                                                                  134.5                                    156                                   180.5-                                                                               2B EtOH                                                                  182.5                                    157                                   129-131                                                                              2B EtOH                            158                                   163-165                                                                              Me.sub.2 CO                        159                                   148-151                                                                              2B EtOH                            160                                   175.5-                                                                               EtOAc                                                                    177.5                                    161                                   170.5-                                                                               Me.sub.2 CO                                                              173.5                                    162                                   130.5-                                                                               95% EtOH                                                                 133.5                                    163                                   166.5-                                                                               Me.sub.2 CO                                                              168                                      164                                   81-90 MeOH                               165                                   154.5-                                                                               Me.sub.2 CO                                                              156                                      166                                   140-  Me.sub.2 CO                                                              141.5                                    167                                   106-110                                                                              95% EtOH                                                                       ether                              168                                   122-  EtOH                                                                     123.5                                    169                                   126.5-                                                                               Acetone                                                                  128.5                                    170                                   135-136                                                                              Acetone                            171                                   148-150                                                                              Acetone                            __________________________________________________________________________

EXAMPLES 172-211

Effective control of acarina larvae is demonstrated in the following tests with larvae of Boophilus microplus, a one-host tick which can remain on a single host through its three life stages, i.e., larvae, nymph and adult. In these tests, a 10% acetone -- 90% water mixture contains from 1.0 to 100 ppm. of test compound. Twenty larvae are enclosed in a pipet sealed at one end with a gauze material and solution containing the test compound is then drawn through the pipet with a vacuum hose simulating a spray system. The ticks are then held for 48 hours at room temperature and mortality is determined. The results achieved are set forth in Table XI below.

                                      TABLE XI                                     __________________________________________________________________________                                                     ppm.                           Example                                                                             Substituents                               Active                                                                               %                        Number                                                                              R    R.sub.1                                                                            R.sub.2                                                                           R.sub.3                                                                            R.sub.4                                                                            W    X      Y     Z    Ingredient                                                                           Mortality                __________________________________________________________________________     172  H    H   O  H   H   H    --OCH.sub.3 (4)                                                                       H     H    100   100                      173  CH.sub.3                                                                            CH.sub.3                                                                           0  H   H   H    --OCH.sub.3 (4)                                                                       H     H    100   100                      174  H    H   O  H   H   Cl (6)                                                                              H      H     Cl (5)                                                                              10    100                      175  CH.sub.3                                                                            CH.sub.3                                                                           O  H   H   Cl (6)                                                                              H      H     Cl (5)                                                                              33    80                       176  H    H   O  H   H   H    benzo (5-6)  H    33    80                       177  H    H   O  H   H   Cl (6)                                                                              H      H     H    33    100                      178  H    H   S  H   H   H    H      H     F (5)                                                                               100   100                      179  H    H   S  H   H   H    H      F (4) H    100   100                      180  CH.sub.3                                                                            CH.sub.3                                                                           O  H   H   Cl (6)                                                                              H      H     H    33    100                      181  H    H   O  H   H   H    --OCH.sub.3 (6)                                                                       H     H    100   100                      182  CH.sub.3                                                                            CH.sub.3                                                                           O  H   H   H    H      H     Cl (5)                                                                              33    100                      183  CH.sub.3                                                                            CH.sub.3                                                                           O  H   H   H    H      CH.sub.3 (6)                                                                         Cl (5)                                                                              33    100                      184  CH.sub.3                                                                            CH.sub.3                                                                           O  H   H   H    CH.sub.3 (4)                                                                          Cl (5)                                                                               Cl (5)                                                                              33    100                      185  CH.sub.3                                                                            CH.sub.3                                                                           O  H   H   Cl (6)                                                                              H      Cl (4)                                                                               H    3.3   100                      186  H    H   O  H   H   H    CH.sub.3 (6)                                                                          Cl (3)                                                                               H    100   80                       187  H    H   O  H   H   H    CH.sub.3 (6)                                                                          CH.sub.3 (3)                                                                         H    33    100                      188  CH.sub.3                                                                            CH.sub.3                                                                           O  H   H   H    CH.sub.3 (6)                                                                          CH.sub.3 (3)                                                                         H    100   50                       189  H    H   O  H   H   H    Cl (5) Cl (3)                                                                               H    10    100                      190  H    H   O  H   H   Cl (6)                                                                              H      CH.sub.3 (4)                                                                         H    33    100                      191  CH.sub. 3                                                                           CH.sub.3                                                                           0  H   H   Cl (6)                                                                              Cl (5) Cl (3)                                                                               Cl (2)                                                                              100   20                       192  H    H   O  H   H   H    CH.sub.3 (5)                                                                          H     Cl (2)                                                                              10    100                      193  H    H   O  H   H   Cl (6)                                                                              Cl (5) Cl (4)                                                                               Cl (3)                                                                              3.3   100                      194  CH.sub.3                                                                            H   O  H   H   H    H      H     H    33    100                      195  phenyl                                                                              H   O  H   H   H    H      H     H    3.3   100                      196  H    H   O  phenyl                                                                             H   H    H      Cl (5)                                                                               Cl (4)                                                                              100   100                      197  CH.sub.3                                                                            CH.sub.3                                                                           O  H   H   Cl (6)                                                                              Cl (5) Cl (4)                                                                               Cl (3)                                                                              100   50                       198  H    phenyl                                                                             O  H   H   Cl (6)                                                                              H      Cl (4)                                                                               H    100   100                      199  H    H   O  H   phenyl                                                                             H    H      H     H    33    100                      200  H    H   O  C.sub.2 H.sub.5                                                                    H   H    H      Cl (4)                                                                               H    10    100                      201  H    H   0  C.sub.2 H.sub.5                                                                    H   H    CH.sub.3 (6)                                                                          Cl (4)                                                                               H    10    100                      202  4-Cl-                                                                               H   O  H   H   H    H      Cl (4)                                                                               H    10    100                           phenyl                                                                    203  CH.sub.3                                                                            H   O  H   H   H    CH.sub.3 (6)                                                                          Cl (4)                                                                               H    100   80                       204  CH.sub.3                                                                            H   O  H   H   H    Cl (6) Cl (4)                                                                               H    10    100                      205  H    H   O  phenyl                                                                             H   H    CH.sub.3 (6)                                                                          Cl (4)                                                                               H    33    100                      206  H    H   S  H   H   H    H      Cl (4)                                                                               H    100   50                       207  CH.sub.3                                                                            CH.sub.3                                                                           S  H   H   H    H      Cl (4)                                                                               H    100   50                       208  CH.sub.3                                                                            H   O  H   H   H    H      Cl (4)                                                                               H    10    100                      209  CH.sub.3                                                                            H   O  H   H   H    Cl (5) Cl (4)                                                                               H    1.0   100                      210  phenyl                                                                              H   O  H   H   H    Cl (5) Cl (4)                                                                               H    33    80                       211  phenyl                                                                              H   O  H   H   H    H      Cl (4)                                                                               H    10    100                      __________________________________________________________________________

EXAMPLES 212-225 Mosquito Egg and Larva Test

Test solutions are prepared in 50% acetone -- 50% water, initially at 1000 ppm. One ml. of 1000 ppm. solution is pipetted into 249 ml. of water in a 400 ml. beaker to yield a 4.0 ppm. test rate. About 100 eggs, 0 to 24 hours old, from Anopheles quadrimaculatus mosquitoes are added inside a wax paper ring floating on the surface of the water. Egg mortality results are noted after two days. Larval mortality results are noted after 3 days. Active compounds are further tested at tenfold dilutions until activity diminishes. The results achieved are set forth in Table XII below.

Ratings:

+ = killed 86% to 100%

± = killed 41% to 85%

0 = killed 0% to 40%

- = not tested

                                      TABLE XII                                    __________________________________________________________________________                                                 Concentration                                                                  in ppm.                                                                        Mosquito                           Example                                                                             Substituents                           Eggs  Larvae                       Number                                                                              R   R.sub.1                                                                            R.sub.2                                                                           R.sub.3                                                                            R.sub.4                                                                           W    X    Y     Z    4  .4 4  .4                        __________________________________________________________________________     212  H   H   O  H   H  H    H    Cl (4)                                                                               H    +  ±                                                                              -  O                         213  H   H   O  H   H  H    Cl (2)                                                                              Cl (4)                                                                               H    O  O  +  +                         214  H   H   O  H   H  H    Cl (3)                                                                              Cl (4)                                                                               H    O  O  +  O                         215  H   H   O  H   H  F (5)                                                                               H    H     H    ±                                                                              O  +  O                         216  H   H   O  H   H  H    H    F (4) H    ±                                                                              O  +  O                         217  H   H   O  H   H  H    H    CH.sub.3 (6)                                                                         Cl (3)                                                                              ±                                                                              O  +  O                         218  CH.sub.3                                                                           CH.sub.3                                                                           O  H   H  H    H    CH.sub.3 (4)                                                                         Cl (3)                                                                              ±                                                                              O  +  O                         219  H   H   O  H   H  H    Cl (3)                                                                              Cl (5)                                                                               H    +  +  ±                                                                              O                         220  H   H   O  H   H  Cl (6)                                                                              Cl (5)                                                                              Cl (4)                                                                               Cl (3)                                                                              ±                                                                              O  +  +                         221  CH.sub.3                                                                           CH.sub.3                                                                           O  H   H  Cl (6)                                                                              Cl (5)                                                                              Cl (4)                                                                               Cl (3)                                                                              +  O  +                            222  H   H   O  C.sub.2 H.sub.5                                                                    H  H    H    Cl (4)                                                                               H    +                                  223  CH.sub.3                                                                           H   O  H   H  H    H    CH.sub.3 (6)                                                                         Cl (4)                                                                              +                                  224  CH.sub.3                                                                           H   O  H   H  H    Cl (4)                                                                              H     H    +                                  225  CH.sub.3                                                                           H   O  H   H  H    Cl (5)                                                                              Cl (4)                                                                               H    +                                  __________________________________________________________________________

EXAMPLES 226-232 Budworm Egg and Larva Test

Test solutions are prepared in 50% acetone -- 50% water, initially at 100 ppm. A one-inch square piece of cheesecloth infested with about 100 eggs of Heliothis virescens is dipped for a second in the solution along with a young cotton leaf. These are allowed to dry and are placed in a covered wax paper cup. Egg mortality ratings are made after 3 days. Larval mortality ratings are made after seven days. Ratings are as shown below in Table XIII.

Ratings:

+ = killed 86% to 100%

± = killed 41% to 85%

0 = killed 0% to 40%

- = not tested

                                      TABLE XIII                                   __________________________________________________________________________                                               Budworm                                                                        Eggs                                                                               Larvae                           Example                                                                             Substituents                         100 100                              Number                                                                              R   R.sub.1                                                                           R.sub.2                                                                           R.sub.3                                                                            R.sub.4                                                                           W    X    Y    Z    ppm.                                                                               ppm.                             __________________________________________________________________________     226  H   H  O  H   H  H    H    Cl (4)                                                                              H    +   -                                227  H   H  O  H   H  H    H    Cl (4)                                                                              Cl (3)                                                                              +   -                                228  H   H  O  H   H  H    Cl (3)                                                                              H    Cl (5)                                                                              ±                                                                               +                                229  CH.sub.3                                                                           H  O  H   H  H    Cl (4)                                                                              H    H    +   -                                230  CH.sub.3                                                                           H  O  H   H  Cl (5)                                                                              Cl (4)                                                                              H    H    +   -                                231  H   H  O  C.sub.2 H.sub.5                                                                    H  H    Cl (4)                                                                              H    H    +   -                                232  p-Cl-                                                                              H  O  H   H  H    Cl (4)                                                                              H    H    +   -                                     phenyl                                                                    __________________________________________________________________________

EXAMPLES 233-235 Mite Egg Test

Cotton plants are infested with mites (Tetranychus urticae) 4 hours before testing to allow egg laying. Plants are dipped in 1000 ppm. solution in 65% acetone/35% water. Adult mortality is noted after 2 days. Egg mortality or mortality of newly hatched nymphs is noted after 7 days. The results achieved are set forth in Table XIV below.

                                      TABLE XIV                                    __________________________________________________________________________                                           %                                        Example                                                                             Substituents                     Mortality                                Number                                                                              R  R.sub.1                                                                           R.sub.2                                                                           R.sub.3                                                                           R.sub.4                                                                           W  X    Y    Z    Mite Eggs                                __________________________________________________________________________     233  H  H  O  H  H  H  Cl (4)                                                                              H    H    100                                      234  H  H  O  H  H  H  Cl (4)                                                                              Cl (2)                                                                              H    100                                      235  H  H  O  H  H  H  Cl (4)                                                                              H    Cl (3)                                                                              100                                      __________________________________________________________________________ 

We claim:
 1. A method for the control of pests selected from the group consisting of insects and acarids as well as the eggs or larvae thereof, comprising contacting said insects, acarids, or eggs or larvae thereof with a pesticidally effective amount of a compound having the formula: ##SPC9##wherein R and R₁ are each selected from the group consisting of hydrogen, lower alkyl (C₁ -C₄), phenyl, halophenyl and benzyl; R₂ is sulfur or oxygen; R₃ and R₄ are each selected from the group consisting of hydrogen, lower alkyl (C₁ -C₄) and phenyl; W is hydrogen or halogen; X is hydrogen, halogen, lower alkyl (C₁ -C₄), halo-substituted lower alkyl (C₁ -C₄), lower alkoxy (C₁ -C₄), lower alkylthio (C₁ -C₄) or nitro; Y is hydrogen, halogen, lower alkyl (C₁ -C₄) or halo-lower alkyl (C₁ -C₄) and Z is hydrogen or halogen.
 2. The method according to claim 1 where R₂ is oxygen.
 3. The method according to claim 1 where R₂ is sulfur.
 4. The method according to claim 2 where R, R₁, R₃, R₄, W, Z and Y are each hydrogen, and X is halogen.
 5. The method according to claim 2 where R, R₁, R₃, R₄, W and Z are each hydrogen, and X and Y are halogen.
 6. The method according to claim 2 where R, R₁, R₃, R₄, W and Z are each hydrogen, X is halogen, and Y is lower alkyl (C₁ -C₄).
 7. The method according to claim 2 wherein eggs or larvae are contacted.
 8. The method according to claim 2 where the compound is: 3'-chloro-2-hydroxy-4,4-dimethyl-6-oxo-1-cyclohexene-1-carboxanilide.
 9. The method according to claim 2 where the compound is: 3',4'-dichloro-3-ethyl-2-hydroxy-6-oxo-1-cyclohexene-1-carboxanilide.
 10. The method according to claim 2 where the compound is: 4'-chloro-2-hydroxy-4-methyl-6-oxo-1-cyclohexene-1-carboxanilide.
 11. The method according to claim 2 where the compound is: 4'-chloro-3-ethyl-2-hydroxy-6-oxo-1-cyclohexene-1-carboxanilide.
 12. The method according to claim 2 where the compound is: 3',4'-dichloro-2-hydroxy-4-methyl-6-oxo-1-cyclohexene-1-carboxanilide.
 13. The method according to claim 2 where the compound is: 4'-bromo-2-hydroxy-6-oxo-1-cyclohexene-1-carboxanilide.
 14. The method according to claim 2 where the compound is: 2-hydroxy-4'-iodo-6-oxo-1-cyclohexene-1-carboxanilide.
 15. The method according to claim 2 where the compound is: 4'-chloro-2-hydroxy-6-oxo-1-cyclohexene-1-carboxanilide. 